Digital Commons Network^™

Catalytic Carbon–Carbon Bond Activation Of Saturated And Unsaturated Carbonyl Compounds Via Chelate-Assisted Coupling Reaction With Indoles, Nuwan Asanka Pannilawithana, Chae S. Yi

Chemistry Faculty Research and Publications

The chelate assistance strategy was devised to promote a highly regioselective catalytic C–C bond activation reaction of saturated and unsaturated carbonyl compounds. The cationic Ru–H complex 1 was found to be an effective catalyst for mediating the coupling reaction of 1,2-disubstituted indoles with α,β-unsaturated aldehydes and ketones, in which the regioselective C_α–C_β activation of the carbonyl substrates has been achieved in forming the 3-alkylindole products. The analogous coupling reaction of indoles with saturated aldehydes and ketones directly led to the C_α–C_β cleavage of the carbonyl substrates in forming the 3-alkylindole products. The coupling reaction …

Using Surface-Enhanced Raman Scattering Of Gold Nanostars For Encoding Molecular Information, Samantha E. Curry

Honors Thesis

Increases in the selling of illicit goods warrant a subsequent need for even more sophisticated methods to prevent counterfeit products from being sold. Surface-enhanced Raman spectroscopy (SERS) has the potential to be a powerful tool to thwart counterfeiters because the unique security tags fabricated with this method are difficult to reproduce without knowing the “secret” recipes used in their preparation. In this work, gold nanostars are used as SERS active substrates since their branched structure allows for strong coupling between the light and plasmonic nanoparticles. As a result, Raman signals of trace amount of chemicals can be easily detected. The …

Structure-Activity Relationship Of Novel Diphenyl Ureas Targeting Mycobacterium, Piper Burghduf

Student Scholars Day Posters

In 2017, the World Health Organization reported that 10 million people were infected with tuberculosis, 1.6 million of whom died. Tuberculosis is caused by a bacterium called Mycobacterium tuberculosis, which primarily infects an individual’s lungs. Unfortunately, failure to adhere to the long and arduous drug regimen has contributed to the emergence of antibiotic-resistant strains of M. tuberculosis. Therefore, the need for novel antibiotics is imperative to saving millions of lives. Our lab has recently developed a family of diphenyl ureas that exhibited increased antimicrobial activity toward Mycobacterium. Reported herein is the continuation of our previous research involving the synthesis of …

Investigating The Role Of Iron-Sulfur Signaling In Yeast Transcriptional Regulation, Malini Gupta

Theses and Dissertations

As an essential cofactor in a myriad of cellular processes, uptake and mobilization of iron must be tightly controlled. Iron homeostasis in fungi involves balancing iron uptake and storage with iron utilization to achieve adequate, non-toxic levels of this essential nutrient. Extensive work in the non-pathogenic yeasts Saccharomyces cerevisiae and Schizosaccharomyces pombe have uncovered unique iron regulation networks for each organism that control iron metabolism via distinct molecular mechanisms. The activities of all fungal iron-sensing transcription factors characterized to date are regulated via iron-sulfur cluster signaling.

In Saccharomyces cerevisiae, expression of iron uptake, utilization and storage genes is primarily regulated …

Current And Future Applications Of 3d Printing Using Custom-Made Materials, Bridger T. Irons

Honors Thesis

The use of 3D printers has increased exponentially from its inception in the 1980s. Recently, the ability to design and create detailed objects has drawn the attention of many who wish to capitalize on this highly customizable process. With much of the focus in this industry being placed on finding new printable materials, many are overlooking the possibility of modifying existing materials. The aim of our research was to modify the materials already being used by 3D printers to alter their properties and explore future possible applications. We examined the addition of graphene powder, carbon microfibers, and other nanoparticles to …

Purification Of Dna Origami Nanostructures Using Capillary Electrophoresis, Janan Hui , '20

Senior Theses, Projects, and Awards

DNA origami are nanostructures designed based on Watson-Crick base-pairing that fold a scaffold into non-arbitrary morphologies using an excess of linear single-stranded DNA "staples". As an engineered nanomaterial (ENM) with great customizability, DNA origami also enjoys the benefit of naturally encoded and well-studied structural and functional properties. The flexibility of different folding patterns allows for construction of a wide variety of shapes and sizes of DNA origami, showing potential applications in fields such as medicine, biocomputing, biomedical engineering , and measurement science. Despite the successes as a functional nanomaterial, a major barrier to the applicability of DNA origami rests in …

Development Of Natural Product-Derived Cationic Polymers For Biomaterial Applications, Moumita Sharmin Jui

Theses and Dissertations

In this thesis, multicyclic natural products and metallocene-containing polymers were synthesized for biomedical applications.

Chapter 1 describes the overall background, the recent development of natural product-based antimicrobial biomaterial and metallocene containing polymer for biomedical application. Afterward, the primary research objectives of my research are illustrated.

In chapter 2, a multicyclic natural product derived guanidine-based facially amphiphilic homopolymers and copolymers were synthesized. Cholic acid is one of the bile acid derivatives used to prepare facially amphiphilic moieties. A neutral polyethylene glycol (PEG) component was used to prepare copolymers with cholic acid. Reversible-addition fragmentation chain transfer (RAFT) polymerization technique was used to …

Quantitative Analysis Of Silver Nanoparticle Dissolution Kinetics In Complex Matrices Using Point-Of-Use And End-Of-Use Models, Daniel J. Boehmler , '20

Senior Theses, Projects, and Awards

Engineered nanomaterials (ENMs) have become increasingly popular for use in both industrial and consumer settings in recent years. Of the myriad of materials used to synthesize ENMs, silver is one of the most common. Silver nanoparticles (AgNPs) undergo dynamic transformations in biological environments, leading to modifications in their reactivity, surface interactions, and speciation. In particular, release of ionic silver (Ag(I)(aq)) through AgNP dissolution can have significant impacts on ecological and human health. Thus, quantifying AgNP dissolution rates in biologically relevant matrices can provide valuable information regarding their potential cytotoxic effects. Linear sweep stripping voltammetry (LSSV) is a technique …

Visible-Light Photooxidation In Water By 1o2-Generating Supramolecular Hydrogels, Sankarsan Biswas, Mohit Kumar, Andrew Levine, Ian Jimenez, Rein V. Ulijn, Adam Braunschweig

Advanced Science Research Center

We report supramolecular photocatalytic hydrogels, produced by the enzymatically driven self-assembly of low molecular weight gelators (LMWGs). These LMWG precursors are composed of the organic chromophore diketopyrrolopyrrole (DPP), which is bi-functionalized with a series of amino acid (Phe, Tyr, Leu) methyl esters. In situ enzymatic hydrolysis of these photoactive precursors results in supramolecular hydrogels that provide a high density of photocatalytic sites. Under visible light irradiation these hydrophobic fibers recruit the reaction substrates and also produce ¹O₂, which is used here for the photooxidation of thioanisole (aromatic substrate) and cyclohexyl methyl sulfide (aliphatic substrate), with yields as …

Versatile Bismuth Salts-Induced Reactions From Our Laboratory: A Perspective, Debasish Bandyopadhyay, Bimal Krishna Banik

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Bismuth salts-mediated reactions are developed for the synthesis of diverse organic molecules of medicinal significance. Reactions conducted with bismuth salts are environmentally friendly and these may proceed due to the release of acids in the media. Bismuth salt may also act as a Lewis acid in these reactions. Versatile organic molecules in chiral and achiral forms are synthesized using bismuth salts-induced reactions at our research laboratory.

Structure–Activity Relationship Of Rgd-Containing Cyclic Octapeptide And Αvβ3 Integrin Allows For Rapid Identification Of A New Peptide Antagonist, Aaron Silva, Wenwu Xiao, Yan Wang, Wei Wang, Heng Wei Chang, James B. Ames, Kit S. Lam, Yonghong Zhang

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

The αvβ3 integrin, a receptor for many extracellular matrix proteins with RGD-sequence motif, is involved in multiple physiological processes and highly expressed in tumor cells, therefore making it a target for cancer therapy and tumor imaging. Several RGD-containing cyclic octapeptide (named LXW analogs) were screened as αvβ3 antagonists with dramatically different binding affinity, and their structure–activity relationship (SAR) remains elusive. We performed systematic SAR studies and optimized LXW analogs to improve antagonistic potency. The NMR structure of LXW64 was determined and docked to the integrin. Structural comparison and docking studies suggested that the hydrophobicity and aromaticity of the X7 amino …

Structural, Functional And Immunological Studies Of Group 1 And 2 House Dust Mite And Profilin Allergens For The Development Of Allergen Specific Diagnostics And Immunotherapy, Anyway B. Kapingidza

Theses and Dissertations

Group 1 and 2 house dust mites (HDM) allergens elicit IgE response in more than 80% of sensitized individuals. These allergens affect 10-30% of the world’s population. Prolonged inhalation of low doses of allergens (microgram amounts inhaled over months or years) by genetically predisposed individuals leads to the induction of a Th2-type immune response induced by allergen-specific immunoglobulin E (IgE) produced by plasma cells resulting in allergic diseases like asthma, atopic dermatitis, and rhinitis. Group 1 and 2 HDM allergens, in particular, are associated with the development of the aforementioned allergic diseases. The goal of this research was to characterize …

Systematic Development Of Photocatalysts, Mary Victoria Bobo

Theses and Dissertations

Photocatalysis is a rapidly growing field and a powerful synthetic tool that has recently seen many advancements, showing immense promise to replace classic catalysis with a mild and elegant alternative methodology. Visible light driven catalysis relies on redox stable transition metal and organic based photoactive catalysts (photocatalysts) that absorb visible light efficiently and facilitate electron/energy transfer. The desire for greener and more renewable catalytic methods has caused research to shifted away from traditional transition metals (due to scarcity and environmental toxicity) and toward organic based photocatalysts. Due to similar photophysical and electrochemical characteristics of each of these classes of photocatalysts …

Synthesis And Characterization Of Novel Derivatives Of 1, 3, 4- 0xadiazole And Isoniazid, Ranem Mohammad Kaddoura

Chemistry Theses

This thesis describes the synthesis of novel derivatives of isoniazid and 1, 3, 4- oxadiazole piperazines and biological activities evaluation. The synthesis of the isoniazid derivatives (36a-Ɩ) was achieved by nucleophilic substitution of chloroacetylated isoniazid 34 with substituted piperazines (35a-Ɩ) produced isoniazidpiperazines (36a-Ɩ). On the other hand, cyclodehydration of chloroacetylated isoniazid 34 with POCl₃ give the corresponding 1, 3, 4-oxadiazole 37 which upon treatment with substituted piperazines (35a-m) gave 1, 3, 4-oxadiazole-piperazines (38a-m). All newly synthesized compounds were purified and characterized using spectroscopic techniques including ¹H-NMR, ¹³C-NMR, IR spectrometry and mass spectrometry.

The biological activity of the …

Chemistry Of A Biscarborane Dithiol And Its Nickel (Ii) Complex, Tyler Hemingway

Theses and Dissertations

Neutral biscarborane dithiol and its anionic dithiolate form were successfully synthesized and structurally characterized. The C–C intracluster bond lengths were found to be responsive to the electron density on the cluster. Introduction of two thiol groups on biscarborane led to the significant increase of intracluster C–C bond lengths compared to those of unsubstituted biscarborane. Furthermore, the anionic dithiolate form had even longer C–C cluster bonds. This comparison shows electronic effect of substituents attached to carbon atoms of biscarborane on the strength of its C–C bonds. Additionally, a novel Ni complex was obtained using this dithiolate as a ligand. This complex …

Hybrid Metal/Covalent Organic Frameworks For Solar Fuel Conversion, Sizhuo Yang

Dissertations (1934 -)

Due to the harsh environment issues such as air pollution and global warming and global energy crisis raised by using fossil fuels, it is urgent to find an alternative sustainable energy source. How to utilize solar energy-the most clean and abundant energy source on earth is challenging. Convert solar energy to clean fuel energy like H2 or hydrocarbons is ideal energy conversion strategy. Thus, design new materials for hydrogen generation or CO2 reduction have attract researcher’s attention.The present study focuses on two types of materials of interest, the first of which is Metal Organic Frameworks (MOFs), including enhancing the …

Theoretical And Experimental Investigation Of Non-Covalent Interactions In S-Nitrosothiols And Thio-Carboxylic Acids, Niloufar Hendinejad

Dissertations (1934 -)

S-Nitrosothiols (RSNOs) are ubiquitous biomolecules whose chemistry is tightly controlled in unknown. In this work, we demonstrate, using high-level ab initio and DFT calculations, the ability of RSNOs to participate in intermolecular interactions with electron pair donors/Lewis bases (LBs) via a σ-hole, a region of positive electrostatic potential on the molecular surface at the extension of the N–S bond. Analysis of the nature of the intermolecular interactions in σ-hole bound RSNO-LB complexes shows the dominant role of electrostatic and dispersion interactions. Importantly, σ-hole binding is able to modulate the properties of RSNOs by changing the balance between two chemically opposite …

Biophysical And Structural Characterization Of Non-Canonical Dna Structures, Linda Yingqi Lin , '20

Senior Theses, Projects, and Awards

Non-canonical DNA structures known as G-quadruplexes (GQs) and i-motifs can form from G-rich and C-rich sequences within the genome, respectively, which are prominent within telomeres and oncogene promoters. These non-canonical quadruplexes likely play roles in regulating gene expression and in DNA replication and repair. However, much remains to be understood about their structural features and diversity. In this work, we investigate the interaction of a GQ-forming sequence with a water-soluble porphyrin, N-methyl mesoporphyrin IX (NMM). Biophysical studies revealed an impressively tight, thermodynamically favorable binding interaction. We then solved the GQ-NMM crystal structure at 2.39 Å, which showed that the DNA …

Development Of Electroanalytical Techniques To Quantify Silver Nanoparticle Dissolution, Aggregation, And Release Kinetics, Zachary J. O'Dell , '20

Senior Theses, Projects, and Awards

Recently, the manufacture of engineered nanomaterials has seen an increase worldwide. This is due to the desirable properties of materials at the nanoscale rather than the bulk scale, such as improved optical, electronic and magnetic properties. Silver nanoparticles (AgNPs) are one of the fastest growing nanomaterials to be incorporated into consumer products due to silver’s well known antibacterial and antimicrobial properties. AgNP-enhanced products represent the largest proportion of engineered nanomaterial products on the consumer market, despite questions regarding the life cycle of such products. AgNPs can undergo a number of transformations during their life cycle including dissolution, aggregation, and protein …

Lignin: A Likely Precursor Of A Significant Fraction Of Humic Substances Via Oxidative Transformations, Seyyedhadi Khatami

Chemistry & Biochemistry Theses & Dissertations

Lignin is a major component of decaying terrestrial vegetation in soils and has been arguably reported to contribute substantially to the formation of soil carbon humus, and natural dissolved organic matter (DOM). To better understand the process by which this humification occurs, lignin and lignin-derived monomers were subjected to both biotic and abiotic oxidation processes. Two well-known oxidative transformation strategies were employed. The first involved the fungal degradation of brown-rot degraded wood subjected to a white-rot fungus (Phanerochaete chrysosporium) whose enzymes are particularly effective in lignin degradation via enzymatic oxidation. This enzymatic attack was monitored by ultrahigh resolution …

Quantum Chemical Lipophilicities Of Antimalarial Drugs In Relation To Terminal Half-Life, Joseph D. Alia, Sheila Karl, Tyler D. Kelly

Chemistry Publications

According to the WHO, artemisinin-based combination therapies (ACTs) have been integral to the recent reduction in deaths due to Plasmodium falciparum malaria. ACT-resistant strains are an emerging problem and have evolved altered developmental stages, reducing exposure of the most susceptible stages to artemisinin drugs in popular ACTs. Lipophilicity, log K_ow, is a guide in understanding and predicting pharmacokinetic properties such as terminal half-life which alters drug exposure. Consistent log K_ow values are not necessarily available for artemisinin derivatives designed to extend terminal half-life, increase bioavailability, and reduce neurotoxicity. For other drugs used in ACTs, an assortment of …

Brown Carbon Production By Aqueous-Phase Interactions Of Glyoxal And So2, David O. De Haan, Kevin Jansen, Alec D. Rynaski, W. Ryan P. Sueme, Ashley K. Torkelson, Eric T. Czer, Alexander K. Kim, Michael A. Rafla, Audrey C. De Haan, Margaret A. Tolbert

Chemistry and Biochemistry: Faculty Scholarship

Oxalic acid and sulfate salts are major components of aerosol particles. Here, we explore the potential for their respective precursor species, glyoxal and SO₂, to form atmospheric brown carbon via aqueous-phase reactions in a series of bulk aqueous and flow chamber aerosol experiments. In bulk aqueous solutions, UV- and visible-light-absorbing products are observed at pH 3–4 and 5–6, respectively, with small but detectable yields of hydroxyquinone and polyketone products formed, especially at pH 6. Hydroxymethanesulfonate (HMS), C₂, and C₃ sulfonates are major products detected by electrospray ionization mass spectrometry (ESI-MS) at pH 5. Past studies …

Dissipation Of Benzobicyclon And Benzobicyclon Hydrolysate In A Louisiana Rice Field, Xavier Poole

LSU Master's Theses

Pesticide resistance in rice fields is an ongoing issue that has resulted in the development and use of pesticides with new modes of action. Benzobicyclon is the first registered hydroxyphenylpyruvate(HPPD)-inhibiting pesticide in the United States and has gained attention as a resistance management strategy to control weed pests in rice fields. Understanding the environmental fate and dissipation mechanisms of benzobicyclon is important due to the unique rotation of rice and crayfish in Louisiana on the same fields. Benzobicyclon persistence into the crayfish growing seasons may lead to unintended consequences for crayfish growth and production, assuming there is toxicity to crawfish. …

The Microbiota-Gut-Brain Axis Heart Shunt Part I: The French Paradox, Heart Disease And The Microbiota, M. Obrenovich, B. Siddiqui, B. Mccloskey, Prakash Reddy

Chemistry Faculty Research & Creative Works

It has been well established that a vegetarian and polyphenol-rich diet, including fruits, vegetables, teas, juices, wine, indigestible fiber and whole grains, provide health-promoting phytochemicals and phytonutrients that are beneficial for the heart and brain. What is not well-characterized is the affect these foods have when co-metabolized within our dynamic gut and its colonizing flora. The concept of a heart shunt within the microbiota-gut-brain axis underscores the close association between brain and heart health and the so-called "French paradox" offers clues for understanding neurodegenerative and cerebrovascular diseases. Moreover, oxidation-redox reactions and redox properties of so-called brain and heart-protective foods are …

Synthesis Of Novel Dicyclohexeno-Crown Ethers With Strategically Incorporated Double Bonds For Further Functionalization, Carim Van Beek, Vincent J. Catalano, Vyacheslav V. Samoshin

Pacific Faculty Work

The number of applications found for crown ether-based materials continues to expand. Many of these applications feature dicyclohexano-18-crown-6 (DC18C6). The number of its derivatives, however, is very limited. To provide a suitable starting structure for the preparation of diverse functionalized DC18C6, the trans-syn-trans and trans-anti-trans isomers of dicyclohexeno-18-crown-6 have been synthesized for the first time through a convenient three-step synthetic procedure, yielding both isomers simultaneously. An efficient chromatographic separation resulted in the isolation of the pure isomers, and single crystal X-ray crystallography determined the solid-state structure of these crown ethers.

Photo-Physical Properties Of Lanthanides Doped O-Bridged Conducting Indole Oligomer, Iffat Ameen, Raj Laxmi Mishra, Abhishek K. Tripathi, Afshan Siddiqui, Umesh N. Tripathi

Karbala International Journal of Modern Science

The indole oligomers were synthesized by an effective green route in the water medium. This is an effort to synthesize commercially important indole oligomers without using any harmful chemicals and artificial media. The lanthanide chlorides such as LaCl₃·7H₂O, CeCl₃·7H₂O, PrCl₃·6H₂O and NdCl₃·6H₂O were used in the synthesis procedure to minimize the reaction time. Unlike the previous works, these reactions occurred at somewhat elevated temperature. In the reaction, the salts of lanthanide metals acted as a catalyst and further behave as dopants. These dopants increased …

Study Of Deformation Parameters (Β2, Δ) For 18,20,22,24,26,28ne Isotopes In Sdpf Shell, Ahmed H. Ali, Maha Taha Idrees

Karbala International Journal of Modern Science

The quadrupole deformation is basic to study the shape transitions; it is possible to predict many important properties of even-even nuclei as a function of the deformation parameter. The deformations of nuclei are important for understanding their shapes prolate or oblate. The quadrupole deformation parameters were calculated by the transition probability B (E2) for ^{18, 20, 22, 24, 26,28}Ne isotopes, were adopted different interactions three. The calculations are performed with the Bohr-Mottelson (B-M) effective charges, which represent the effect of the core-polarizations. Also, the deformation parameters were calculated for different nuclei and adopted two methods of calculation: from reduced …

Investigation Of Glucose Oxidation At Gold Nanoparticles Deposited At Carbon Nanotubes Modified Glassy Carbon Electrode By Theoretical And Experimental Methods., Farhat Saira, Humaira Razzaq, Misbah Mumtaz, Safeer Ahmad, Muhammad Aftab Rafiq, Azra Yaqub, Nabiha Dilshad, Ayesha Ihsan, Muhammad Masood Ul Hasan

Karbala International Journal of Modern Science

In the current research work, AuNPs-CNTs nanocomposite was synthesized chemically and decoration of AuNPs on the surface of MWCNTs was confirmed by UV-Vis, SEM and XPS analysis. Synthesized nanocomposite was utilized for its application towards non-enzymatic glucose sensing by modifying glassy carbon electrode with nanocomposite employing electrochemical techniques. In addition, theoretical calculations were performed by Density Functional Theory (DFT), employing B3YLP with basis set 6- 311+G(d,p) in gaseous phase and LANL2DZ basis set. Both theoretical and experimental results predicted Au-CNTs composite as a better candidate for glucose oxidation as compared to CNTs and AuNPs alone, owing to the synergistic effect …

A Study To Explore The Ldlr Gene Polymorphisms Contribute To Atorvastatin Response In A Sample Of Iraqi Population With Atherosclerotic Coronary Artery Disease, Shaimaa Y. Abdulfattah, Salwa J. Abdullah, Hilal B. Alsaffar

Karbala International Journal of Modern Science

Genetic factors will determine the higher variability, which found in response to lipid reduction treatment (statins). However, due to ethnicity the frequency and effect of single nucleotide polymorphisms (SNPs) may differ. The main aim of lipid lowering medical treatment is to eventually prevent the endogenous production of cholesterol through inhibition of HMG-CoA reductase, The resulting decrease in hepatocyte cholesterol concentration triggers up-regulation of low-density lipoprotein (LDL)-receptor expression by inducing sterol regulatory element-binding protein (SREBP) 2 cleavage, as SREBP-2 activates LDL receptor transcription. The aim of this study was to evaluate the effects of low density lipoprotein receptor (LDL-R) …

Using Freak Descriptor To Classify Plasma Influence In Mice Sperm, Ekhlas Falih, Alaa Noori Mazhar

Karbala International Journal of Modern Science

Numerous classification mechanisms anticipate the class's instances to be carried out as the features' vectors, namely the points in a feature's space. It is oftentimes a chance to make an informative exemplification of an image's feature vector for classification problems in computer vision like utilizing global descriptors for the texture description or shape description. The proposed methodology is to classify the sperm image in mice that has been affected through plasma and this methodology consists of three stages. The points of interest could be elicited from sperm plasma images in the first stage by utilizing Adaptive and Generic Corner detector …